JP2002030033A - cis-DICYCLOHEXYL-3,3'4,4'-TETRACARBOXYLIC ACID, ITS DIANHYDRIDE AND METHOD FOR PRODUCING THEM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cis-dicyclohexy1-3,3'4,4-tetracarboxylic acid and a cis- dicyclohyxyl-3,3'4,4'-tetracarbosylic acid dianhydride being new starting raw materials for a polyimide resin. SOLUTION: (1R,1'S,3R,3'S,4S,4'R)-Dicyclohexyl-3,3'4,4'-tetracarbosylic acid and (1R, 1'S,3R,3'S,4S,4'R)-dicyclohexyl-3,3'4,4'-tetracarboxylic acid dianhydride are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel substance (1R, 1'S, 3R, 3'S, 4S, 4'R) -dicyclohexyl-3,3'4,4'-tetracarboxylic acid ( Hereinafter, it may be abbreviated as cis-DCTA-x.)
And (1R, 1'S, 3R, 3'S, 4S, 4'R)
-Dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride (hereinafter sometimes abbreviated as cis-DCDA-x).

[0002]

2. Description of the Related Art Tetracarboxylic acids are compounds useful as precursors of tetracarboxylic dianhydride, which is a raw material for polyimide resins having excellent heat resistance. The conversion of a benzene ring to the corresponding cyclohexane ring by hydrogen reduction is well known and is described, for example, in a synthetic command.
unication, 25 , 2079 (1995), JP-A-10-36320, JP-A-11-189568.
JP-A-11-349535, JP-A-10-204
No. 002 and Tokuhei 8-30045 have been reported.

[0003] When hydrogen reduction of tetramethyl biphenyl-3,3'4,4'-tetracarboxylate (abbreviated as BPTM) results in the product having six asymmetric carbons,
^Six isomers are possible. The hydrogen reduction of BPTM is also described in JP-A-7-215912 and JP-A-8-3251.
No. 96 and JP-A-8-325201 have been reported, but these reports do not mention this isomer at all and only refer to mixtures.

[0004] A reaction formula for producing an isomer by hydrogen reduction of BPTM is shown below. (In the formula, Me represents a methyl group.)

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[0005]

According to these reports, this mixture is hydrolyzed without separation to synthesize a mixture of tetracarboxylic acids, and further, anhydrous to synthesize a mixture of tetracarboxylic dianhydrides. I have. Although it is valuable to isolate a particular isomer from a large mixture of isomers, it is not yet known. Accordingly, an object of the present invention is to provide a tetracarboxylic acid composed of a specific isomer, a dianhydride thereof, and a production method thereof.

[0006]

According to the present invention, (1R,
1 ′S, 3R, 3 ′S, 4S, 4′R) -dicyclohexyl-3,3′4,4′-tetracarboxylic acid, and (1R, 1 ′S, 3R, 3 ′S, 4S, 4 ′) R) -Dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride.

Further, the present invention relates to (1R, 1'S, 3
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
Hydrolyzes tetramethyl 3'4,4'-tetracarboxylate (1R, 1'S, 3R, 3'S, 4S, 4'R)
-Dicyclohexyl-3,3'4,4'-tetracarboxylic acid. Further, the present invention provides (1R,
1 ′S, 3R, 3 ′S, 4S, 4′R) -Dicyclohexyl-3,3′4,4′-tetracarboxylate is hydrolyzed to tetracarboxylic acid, which is dehydrated. (1R, 1'S, 3R, 3'S, 4S, 4 '
The present invention relates to a method for producing R) -dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride.

In the present invention, (1R, 1'S, 3R,
3'S, 4S, 4'R) -Dicyclohexyl-3,3 '
For the isolation and confirmation of 4,4′-tetramethyl (abbreviated as cis-DCTM-x), refer to Japanese Patent Application No. 2000-1.
A patent application has been filed as 91050.

The hydrolysis of the tetramethyl ester is carried out with heated water or in the presence of an alkali or an acid catalyst, and after dissolving tetramethyl in a solvent, heating and adding water to remove methanol. -Removes oil and water. In the hydrolysis in the presence of an alkali catalyst, the solvent to be used may be any solvent that can dissolve a tetramethyl ester such as n-butanol and propanol.

The amount of the solvent used is cis-DCTM-x
Requires a sufficient amount to dissolve
-40-100 mL per 10 g of DCTM-x.
It is not particularly necessary to use an excess of the solvent, but if the amount is too small, the reaction does not proceed or the hydrolysis is incomplete. As the alkali catalyst, use may be made of, for example, caseiso-da, caesari, and the like, and the use amount thereof is preferably 4 to 8 equivalents per 1 mol of cis-DCTM-x. If the amount is less than 4 equivalents, hydrolysis may be incomplete. Usually, it is preferred to use an excess amount to complete the hydrolysis.

The reaction time is 0.5 to 10 hours, preferably 1 to 4 hours. Thereafter, methanol and the water to be eliminated are removed while adding water. After completion of the reaction, it is dissolved in water as an alkali salt, but if the amount of water is small, the alkali salt may be precipitated. Usually 100mL of water per 10g
If it is, it is a homogeneous solution. When an acid such as concentrated hydrochloric acid is added to the solution to make it acidic, tetracarboxylic acid is precipitated.
This is washed with water to obtain the desired product.

In the hydrolysis in the presence of an acid catalyst, the solvent to be used may be any one which dissolves a tetramethyl ester such as acetic acid or propionic acid and which can be transesterified. The amount used must be sufficient to dissolve cis-DCTM-x, for example, cis-DCTM
20-100 mL per x10 g. It is not particularly necessary to use an excess of the solvent, but if the amount is too small, the reaction does not proceed or the hydrolysis is incomplete. As the acid catalyst, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like can be used. The reaction time is 0.5 to 10 hours, preferably 3 to
The reaction is carried out for 6 hours, after which the methyl carboxylate and water which are eliminated are removed while adding water. As the reaction proceeds, tetracarboxylic acid precipitates. This is washed with water to obtain the desired product (1R, 1'S, 3R, 3'S, 4S, 4'R) -dicyclohexyl-3,3'4,4'-tetracarboxylic acid.

In order to dehydrate the above tetracarboxylic acid, the tetracarboxylic acid is dehydrated and cyclized using acetic anhydride, propionic anhydride, acetyl chloride or the like. The use amount of these dehydrating agents is preferably 2 to 100 equivalents, particularly preferably 30 to 80 equivalents, per 1 mol of cis-DCTA-x. If it is less than 2 equivalents, the dehydration may be incomplete. Usually, it is preferable to use an excess amount to complete the dehydration. Reaction temperature is 50-1
The reaction is preferably performed at 50 ° C. for a reaction time of 0.5 to 10 hours, particularly 3 to 7 hours.

The (1R, 1'S, 3R, 3 ') of the present invention
(S, 4S, 4'R) -Dicyclohexyl-3,3'4
The chemical formula of 4′-tetracarboxylic acid (cis-DCTA-x) is shown below.

[0015]

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Further, in the present invention, (1R, 1 ′)
S, 3R, 3'S, 4S, 4'R) -Dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride (ci
The chemical formula of (s-DCDA-x) is shown below.

[0017]

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[0018]

Embodiments of the present invention will be described below. High performance liquid chromatography: Shimadzu SCL-10A, column: Ch
iralcel OD (Daicel Chemical Industries) 0.46c
mφ, 25cm, 20 ° C, EtOH / n-hexane
(10/90), measured at 0.5 mL / min. ¹
HNMR spectrum (400 MHz) is available from JEOL JE
OL 400X, DMSO-d ₆ solution was measured at 25 ° C.. ^{The 13} C NMR spectrum (100 MHz) was measured at 25 ° C. in JEOL JEOL 400X, DMSO-d ₆ solution. The FTIR spectrum is JEOL JIR-550.
It was measured by the 0KBr tablet method.

Synthesis Example 1 100 g of BPT in a 500 mL rotating autoclave
M, 2.5 g of 5% Rh / C, and 200 mL of tetrahydrofuran were charged and heated at 100 ° C. under a constant pressure of 30 kg / cm ² of hydrogen at 300 rpm for 5.5 hours (the absorption of hydrogen was completed in about 5 hours) ). After the reaction solution was filtered using No. 5c filter paper, tetrahydrofuran was distilled off to obtain 101.8 g (yield 99%) of a viscous product.
This was dissolved in 400 mL of methanol and crystallized to obtain 72 g of cis-DCTM. 100g ci
s-DCTM (x / (y + z) = 51/49)
Dissolved in mL of tetrahydrofuran and slowly crystallized. The crystals were separated and tetrahydrofuran (1: 2
Ratio), the crystallization was repeated three times to obtain 100% pure cis.
-DCTM-x (8.5 g) was obtained.

Synthesis Example 2 50 g of cis-DCTM (x / (y + z) during crystallization)
= 60/40) in 100 mL of tetrahydrofuran and slowly crystallized. The crystals were separated and crystallized again from tetrahydrofuran (1: 2 ratio) to obtain 100% pure cis-DCTM-x (11.6 g).

Example 1 A 300 mL three-necked flask was equipped with a stirrer and a reflux condenser, and 10 g of cis-DCTM-x (25.1) was added thereto.
mM) and 50 mL of n-butanol were dissolved by heating. 64 g (161 mM) of a 10% aqueous NaOH solution was added, and the mixture was refluxed for 3 hours. After that, replace with a Liebig condenser and add 150 mL of water while adding n-butanol.
, Desorbed methanol and water were distilled off (total of 160
mL). Once filtered, the filtrate was 100 mL. When 14 mL of concentrated hydrochloric acid was added to the aqueous solution to adjust the pH to 1, a white precipitate was deposited. The mixture was filtered, washed with water, and washed until no Cl ion was detected. Vacuum dried at 100 ° C., 7.3
5 g of product was obtained (86% yield). The elemental analysis values are shown below. C ₁₆ H ₂₂ O ₈ (342.35): Calculated value, C 56.1.
H 6.5, found, C 55.9, H 6.4, m
p: 248-250 ° C, IR, ν (CO): 1705
cm ^-1 in Figure 1 to ¹ HNMR and Figure 2 shows the ¹³ CNMR.

Example 2 A 300 mL three-necked flask was equipped with a stirrer and a reflux condenser, and 10 g of cis-DCTM-x (25.1) was added thereto.
mM) and 25 mL of acetic acid and dissolved by heating. 25m water
L and 10 mL of concentrated hydrochloric acid were added, and the mixture was refluxed for 4 hours. Two hours later, a white precipitate was partially observed. Thereafter, the mixture was replaced with a Liebig condenser, and methyl acetate and water were distilled off while adding 350 mL of water (total of 370 mL). Filtration, washing with water and vacuum drying at 100 ° C. yielded 6.67 g of product (yield 78%).

Example 3 10 g of cis-DCTA-x obtained in Example 1 was placed in a round-bottom flask and refluxed with 300 mL of acetic anhydride for 3 hours (homogeneous solution). The crystals precipitated by cooling in a refrigerator were filtered and dried in vacuum at 100 ° C. to obtain 6.82 g of a product (yield: 75%). The target substance can be further recovered by partially concentrating the filtrate. The elemental analysis values are shown below. C ₁₆ H ₁₈ O ₆ (306.32): calculated value, C 62.7,
H5.9, experimental, C62.7, H5.9, m
p: 246-248 ° C, IR, ν (CO): 186
^1, 1780 cm ^-1 FIG. 3 shows ¹ HNMR and FIG. 4 shows ¹³ CNMR.

Example 4 cis-DCTA obtained in Example 1
-Transfer 3.0 g to a round bottom flask and add 45 mL of acetic anhydride
For 3 hours (heterogeneous). After cooling in a refrigerator, the crystals were filtered and dried at 100 ° C. under vacuum to obtain 2.29 g of the product (yield: 85%).

[Confirmation of Structure of cis-DCTA-x by NMR] When attention is paid to protons at the 3, 4 and 3 ', 4' positions in ¹ HNMR of cis-DCTA-x (FIG. 1),
The peak at 3.00 ppm has small splitting, which is due to the two protons (A) at the equatorial position and 2.34 ppm.
The peak of pm was greatly split and was assigned to two protons (B) at the axial position. This proton B is a double triplet (J (BF) = 12.2 Hz, J (BE) = J
(BA) = 3.4 Hz). In addition, two-dimensional HH
From the COSY spectrum and the CH COSY spectrum, protons and carbons of the cyclohexane ring were assigned.

[Confirmation of NMR Structure of cis-DCDA-x] FIG. 5 shows an enlarged view of protons at the 3,4 and 3 ′, 4 ′ positions in ¹ HNMR of cis-DCDA-x (FIG. 3). Was. Focusing on the protons at the 3,4 and 3 ', 4'-positions, the peak at 3.50 ppm is now double triplet (J (AB) = J (AD) = 7.3 Hz, J
(AC) = 2.9 Hz). It is thought to be the effect of the anhydrous ring. This was assigned to two protons (A) at the equatorial position. The peak at 3.13 ppm had a large splitting and was assigned to two protons (B) at the axial position. This proton B is a double quartet (J (B
F) = 11.6 Hz, J (BA) = 7.3 Hz, J (B
E) = 8.2 Hz). Note that two-dimensional H-H C
From the OSY spectrum and the CH COSY spectrum, the protons and carbons of the cyclohexane ring were assigned. These results are shown in Table 1 ( ¹ HNMR) and Table 2 (
¹³ C NMR).

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

According to the present invention, tetracarboxylic dianhydride 1R, 1'S,
3R, 3'S, 4S, 4'R) -Dicyclohexyl-
3,3'4,4'-tetracarboxylic dianhydride (cis
-DCDA-x) and 1R useful as precursors thereof,
1 ′S, 3R, 3 ′S, 4S, 4′R) -Dicyclohexyl-3,3′4,4′-tetracarboxylic acid (cis-
DCTA-x) and their preparation.

[Brief description of the drawings]

FIG. 1 shows 1R, 1 ′S, 3 obtained in Example 1.
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
3'4,4'-tetracarboxylic acid (cis-DCTA-
It is a ¹ HNMR of x).

FIG. 2 shows 1R, 1 ′S, 3 obtained in Example 1.
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
3'4,4'-tetracarboxylic acid (cis-DCTA-
It is ¹³ CNMR of x).

FIG. 3 shows 1R, 1 ′S, 3 obtained in Example 3.
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
3'4,4'-tetracarboxylic dianhydride (cis-D
¹ H NMR of CDA-x).

FIG. 4 shows 1R, 1 ′S, 3 obtained in Example 3.
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
3'4,4'-tetracarboxylic dianhydride (cis-D
It is ¹³ CNMR of CDA-x).

FIG. 5 shows 1R, 1 ′S, 3R, 3 ′S, 4S,
¹ H of 4′R) -dicyclohexyl-3,3′4,4′-tetracarboxylic dianhydride (cis-DCDA-x)
FIG. 3 is an enlarged view of protons at positions 3, 4 and 3 ′, 4 ′ in NMR.

Claims (4)

[Claims] (1R, 1'S, 3R, 3'S, 4S,
4'R) -Dicyclohexyl-3,3'4,4'-tetracarboxylic acid. 2. The method according to claim 1, wherein (1R, 1'S, 3R, 3'S, 4S,
4'R) -Dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride. 3. The method of claim 1, wherein (1R, 1'S, 3R, 3'S, 4S,
Hydrolyzes 4′R) -dicyclohexyl-3,3′4,4′-tetramethyl tetracarboxylate (1R, 1 ′
A method for producing (S, 3R, 3'S, 4S, 4'R) -dicyclohexyl-3,3'4,4'-tetracarboxylic acid. 4. The method according to claim 1, wherein (1R, 1'S, 3R, 3'S, 4S,
Hydrolysis of tetramethyl 4′R) -dicyclohexyl-3,3′4,4′-tetracarboxylate to a tetracarboxylic acid, which is then dehydrated (1R, 1 ′S, 3)
R, 3'S, 4S, 4'R) -Dicyclohexyl-3
Process for producing 3'4,4'-tetracarboxylic dianhydride.